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JP2019055414A - Joint material - Google Patents

Joint material Download PDF

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Publication number
JP2019055414A
JP2019055414A JP2017181702A JP2017181702A JP2019055414A JP 2019055414 A JP2019055414 A JP 2019055414A JP 2017181702 A JP2017181702 A JP 2017181702A JP 2017181702 A JP2017181702 A JP 2017181702A JP 2019055414 A JP2019055414 A JP 2019055414A
Authority
JP
Japan
Prior art keywords
bonding material
metal particles
melting point
point metal
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2017181702A
Other languages
Japanese (ja)
Inventor
真浩 坂田
Masahiro Sakata
真浩 坂田
真樹 山口
Maki Yamaguchi
真樹 山口
斉藤　晃一
Koichi Saito
晃一 斉藤
雅記 竹内
Masaki Takeuchi
雅記 竹内
史貴 上野
Fumitaka Ueno
史貴 上野
安　克彦
Katsuhiko Yasu
克彦 安
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Motor Corp
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Toyota Motor Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd, Toyota Motor Corp filed Critical Hitachi Chemical Co Ltd
Priority to JP2017181702A priority Critical patent/JP2019055414A/en
Priority to CN201811042895.XA priority patent/CN109530957A/en
Priority to US16/127,464 priority patent/US20190084093A1/en
Publication of JP2019055414A publication Critical patent/JP2019055414A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • B23K35/286—Al as the principal constituent
    • B23K35/288—Al as the principal constituent with Sn or Zn
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
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    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3006—Ag as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3013—Au as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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    • B23K35/302—Cu as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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    • B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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    • B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
    • B23K35/3613—Polymers, e.g. resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/362—Selection of compositions of fluxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L24/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/341—Surface mounted components
    • H05K3/3431—Leadless components
    • H05K3/3436—Leadless components having an array of bottom contacts, e.g. pad grid array or ball grid array components
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • H05K3/3431—Leadless components
    • H05K3/3442—Leadless components having edge contacts, e.g. leadless chip capacitors, chip carriers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
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    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces
    • H—ELECTRICITY
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Abstract

To provide a joint material in which a whisker is hard to occur.SOLUTION: A joint material disclosed herein contains a high melting metal particle, a low melting metal particle, and a flux resin having a thermosetting property. A mass ratio of the high melting metal particle to a gross mass of the high melting metal particle and the low melting metal particle is 55 to 75%. Further, it is preferable that the mass ratio of the high melting metal particle falls within a range of 65 to 75%. The high melting metal particle is any one of Cu, Cu alloy, Al, Ag, and Au, and a particle diameter thereof is preferably 5 to 30 μm. The low melting metal particle is Sn alloy, and a particle diameter thereof is preferably 20 to 40 μm.SELECTED DRAWING: None

Description

本明細書が開示する技術は、接合材に関する。特に、ウィスカが発生し難い接合材に関する。   The technology disclosed in this specification relates to a bonding material. In particular, the present invention relates to a bonding material in which whisker hardly occurs.

銅（Ｃｕ）などの高融点金属粒子と、スズ合金（Ｓｎ合金）などの低融点金属粒子を混合した接合材（はんだ材）が知られている（例えば特許文献１、２）。そのような接合材は、遷移的液相焼結法（Transient Liquid Phase Sintering; TLPS）に適している。上記の接合材は、半導体モジュールの基板への実装など、２回のリフロー工程が必要な実装工程の１次リフローに用いられる。   There is known a bonding material (solder material) in which high melting point metal particles such as copper (Cu) and low melting point metal particles such as tin alloy (Sn alloy) are mixed (for example, Patent Documents 1 and 2). Such a bonding material is suitable for the Transient Liquid Phase Sintering (TLPS) method. The bonding material is used for primary reflow in a mounting process that requires two reflow processes, such as mounting a semiconductor module on a substrate.

特開２００２−２５４１９４号公報JP 2002-254194 A 特開２００２−２６１１０５号公報JP 2002-261105 A

接合材を用いる場合、ウィスカの抑制が課題である。本明細書が開示する技術は、高融点金属粒子と低融点金属粒子の配合比を限定するとともに、熱硬化性を有するフラックス樹脂を配合することで、ウィスカを抑制することのできる接合材を提供する。   When using a bonding material, suppression of whiskers is a problem. The technology disclosed in this specification provides a bonding material capable of suppressing whisker by limiting the blending ratio of high melting point metal particles and low melting point metal particles and blending a thermosetting flux resin. To do.

本明細書が開示する接合材は、高融点金属粒子と、低融点金属粒子と、熱硬化性を有するフラックス樹脂を含んでいる接合材である。「高融点金属」とは、「低融点金属」との比較で融点が高い金属を意味する。なお、高融点金属は、特に、Ｓｎ−Ａｇ−Ｃｕ系の接合材の融点よりも高いことが望ましい。「低融点金属」とは、「高融点金属」との比較で融点が低い金属を意味する。高融点金属粒子と低融点金属粒子の総質量に対する高融点金属粒子の質量割合は、５５〜７５％である（したがって、低融点金属粒子の質量割合は４５〜２５％となる）。   The bonding material disclosed in this specification is a bonding material including high melting point metal particles, low melting point metal particles, and a thermosetting flux resin. “High melting point metal” means a metal having a higher melting point than “low melting point metal”. Note that the refractory metal is particularly preferably higher than the melting point of the Sn—Ag—Cu based bonding material. “Low melting point metal” means a metal having a lower melting point than “high melting point metal”. The mass ratio of the high melting point metal particles to the total mass of the high melting point metal particles and the low melting point metal particles is 55 to 75% (therefore, the mass ratio of the low melting point metal particles is 45 to 25%).

上記の質量割合と、熱硬化性を有するフラックス樹脂の配合により、ウィスカの原因となるＳｎ成分は全て高融点金属との合金化に使われ、リフロー後にＳｎ成分は残存しなくなる。それゆえ、ウィスカの発生を抑制することができる。高融点金属粒子の質量割合が５５％未満であると、焼結後に低融点金属が残存する。残存する低融点金属はウィスカの発生要因となる。他方、高融点金属粒子の質量割合が７５％を超えると、接合材の全体に合金化が進行せず、接合強度不足を生じるおそれがある。なお、高融点金属粒子の質量割合は、６５〜７５％であることが好ましい。そのような範囲であると、ウィスカの抑制効果と、接合強度の点でバランスがよい。実施例において、ウィスカ抑制効果を確かめた試験の結果を示す。   Due to the blending of the above mass ratio and thermosetting flux resin, all Sn components that cause whiskers are used for alloying with refractory metals, and Sn components do not remain after reflow. Therefore, the generation of whiskers can be suppressed. When the mass ratio of the high melting point metal particles is less than 55%, the low melting point metal remains after sintering. The remaining low melting point metal becomes a cause of whisker generation. On the other hand, if the mass ratio of the refractory metal particles exceeds 75%, alloying does not proceed to the entire bonding material, which may result in insufficient bonding strength. In addition, it is preferable that the mass ratio of a refractory metal particle is 65 to 75%. Within such a range, there is a good balance in terms of whisker suppression effect and bonding strength. In an Example, the result of the test which confirmed the whisker suppression effect is shown.

本明細書が開示する技術の詳細とさらなる改良は以下の「発明を実施するための形態」にて説明する。   Details and further improvements of the technology disclosed in this specification will be described in the following “DETAILED DESCRIPTION”.

接合材のイメージ図である（焼結前）。It is an image figure of a joining material (before sintering). 接合材のイメージ図である（焼結後）。It is an image figure of a joining material (after sintering). 接合材を用いた部品実装工程を説明する図である。図３（Ａ）は、ペースト状の接合材の印刷工程を説明する図である。図３（Ｂ）は、部品の載置工程を説明する図である。図３（Ｃ）は、リフロー工程を説明する図である。It is a figure explaining the component mounting process using a joining material. FIG. 3A is a diagram illustrating a printing process of a paste-like bonding material. FIG. 3B is a diagram illustrating a component placing process. FIG. 3C illustrates the reflow process. 接合材の評価試験の結果を示す表である（１）。It is a table | surface which shows the result of the evaluation test of a joining material (1). 接合材の評価試験の結果を示す表である（２）。It is a table | surface which shows the result of the evaluation test of a joining material (2).

本明細書が開示する接合材は、遷移的液相焼結法を利用した導電性接合材であり、２６０℃以下の温度でリフローすることで焼結が可能である。この接合材は、焼結後は、２６０℃では再溶融せず、また、ウィスカの発生を抑制できる。本明細書が開示する接合材によれば、従来よりも１次リフローの低温化が可能である。また、本明細書が開示する接合材は、ウィスカの発生を抑えることができる。即ち、焼結後に長時間放置しても導電性のひげが発生しない。それゆえ、焼結後の合金の表面に絶縁樹脂等のコーティング剤を塗布するなどの絶縁対策が不要となる。   The bonding material disclosed in this specification is a conductive bonding material using a transitional liquid phase sintering method, and can be sintered by reflowing at a temperature of 260 ° C. or lower. This bonding material does not remelt at 260 ° C. after sintering and can suppress the generation of whiskers. According to the bonding material disclosed in the present specification, it is possible to lower the temperature of the primary reflow than in the past. Further, the bonding material disclosed in this specification can suppress the generation of whiskers. That is, even if it is left for a long time after sintering, conductive whiskers do not occur. Therefore, it is not necessary to take insulation measures such as applying a coating agent such as an insulating resin to the surface of the sintered alloy.

本明細書が開示する接合材の技術要素を以下に記す。なお、以下の技術要素は、それぞれ独立した技術要素であって、単独であるいは各種の組合せによって技術的有用性を発揮するものであり、出願時請求項記載の組合せに限定されるものではない。   The technical elements of the bonding material disclosed in this specification will be described below. The following technical elements are independent technical elements and exhibit technical usefulness alone or in various combinations, and are not limited to the combinations described in the claims at the time of filing.

本明細書が開示する複合材のイメージを図１と図２に示す。図１は、焼結前の接合材１０ａのイメージ図であり、図２は、焼結後の接合材１０ｂのイメージ図である。焼結前の接合材１０ａでは、高融点金属粒子１２と、低融点金属粒子１３ａと、熱硬化性を有するフラックス樹脂１４ａを含んでいる。高融点金属粒子１２は、例えば、粒径が５〜１５μｍのＣｕ粒子である。低融点金属粒子１３ａは、例えば、粒径が２０〜４０μｍのＳｎ合金である。高融点金属粒子１２と低融点金属粒子１３ａの総質量に対する高融点金属粒子１２の質量割合は、例えば６５％である。フラックス樹脂１４ａは、流動性を有しており、高融点金属粒子１２と低融点金属粒子１３ａを包み込んでいる。フラックス樹脂１４ａが流動性を有しているので、焼結前の接合材１０ａは、ペースト状である。   An image of the composite material disclosed in this specification is shown in FIGS. FIG. 1 is an image diagram of the bonding material 10a before sintering, and FIG. 2 is an image diagram of the bonding material 10b after sintering. The bonding material 10a before sintering includes the high melting point metal particles 12, the low melting point metal particles 13a, and a thermosetting flux resin 14a. The refractory metal particles 12 are, for example, Cu particles having a particle size of 5 to 15 μm. The low melting point metal particle 13a is, for example, a Sn alloy having a particle size of 20 to 40 μm. The mass ratio of the high melting point metal particles 12 to the total mass of the high melting point metal particles 12 and the low melting point metal particles 13a is, for example, 65%. The flux resin 14a has fluidity and encloses the high melting point metal particles 12 and the low melting point metal particles 13a. Since the flux resin 14a has fluidity, the bonding material 10a before sintering is pasty.

焼結後の接合材（図２）では、低融点金属粒子は溶融し、高融点金属粒子の一部と合金化する。図２の符号１３ｂが、合金を表している。固まった合金１３ｂは、高融点金属の残留粒子の全体を覆っており、焼結後の接合材１０ｂは焼結する。また、フラックス樹脂１４ｂは熱硬化する。ウィスカの原因となる低融点金属（図１の低融点金属粒子１３ａ）は、全て合金に使われるので、ウィスカが発生しない。   In the bonding material after sintering (FIG. 2), the low melting point metal particles are melted and alloyed with a part of the high melting point metal particles. The code | symbol 13b of FIG. 2 represents the alloy. The solidified alloy 13b covers the entire residual particles of the refractory metal, and the sintered bonding material 10b is sintered. Further, the flux resin 14b is thermoset. Since the low melting point metal (low melting point metal particles 13a in FIG. 1) that causes whisker is all used in the alloy, no whisker is generated.

高融点金属粒子は、Ｓｎ−Ａｇ−Ｃｕ系の接合材よりも融点が高い金属（金属合金）であればよい。高融点金属粒子は、Ｃｕ、Ｃｕ合金、Ａｌ、Ａｇ、Ａｕのいずれかであり、その粒径が５〜３５μｍであるとよい。高融点金属粒子は、特にＣｕ粒子であることが望ましい。また、粒子径が５μｍ未満であると、粒子の凝集力が上昇し、接合材のペーストを製造する際、粘度が高くなりすぎるおそれが生じる。他方、粒径が３０μｍを超えると、接合材中の金属密度が低下するため、接合強度不足のおそれが生じる。なお、本明細書が開示する接合材は、高融点金属粒子として、Ｃｕ、Ｃｕ合金、Ａｌ、Ａｇ、Ａｕのいずれか１種類の金属のみを含むものであってもよいし、複数種類の金属を含むものであってもよい。高融点金属粒子の表面がＳｎまたはＳｎ合金でめっきされていてもよい。   The high melting point metal particles may be any metal (metal alloy) having a melting point higher than that of the Sn—Ag—Cu based bonding material. The refractory metal particles are any one of Cu, Cu alloy, Al, Ag, and Au, and the particle size is preferably 5 to 35 μm. The refractory metal particles are particularly preferably Cu particles. Further, when the particle diameter is less than 5 μm, the cohesive force of the particles is increased, and when the paste for the bonding material is produced, there is a possibility that the viscosity becomes too high. On the other hand, when the particle size exceeds 30 μm, the metal density in the bonding material is lowered, which may result in insufficient bonding strength. Note that the bonding material disclosed in the present specification may contain only one kind of metal of Cu, Cu alloy, Al, Ag, and Au as the high melting point metal particles, or a plurality of kinds of metals. May be included. The surface of the refractory metal particles may be plated with Sn or an Sn alloy.

低融点金属粒子は、Ｓｎ合金であればよいが、Ｓｎ−Ａｇ系、Ｓｎ−Ａｇ−Ｃｕ系、Ｓｎ−Ｉｎ−Ａｇ−Ｂｉ系、Ｓｎ−Ｚｎ系、Ｓｎ−Ｚｎ−Ｂｉ系、Ｓｎ−Ｂｉ系、Ｓｎ−Ｉｎ系などの中温系から低温系のはんだ材であることが望ましい。本明細書が開示する接合材は、低融点金属粒子として、１種類のＳｎ合金のみを含むものであってもよいし、複数種類のＳｎ合金を含むものであってもよい。   The low melting point metal particles may be Sn alloys, but Sn—Ag, Sn—Ag—Cu, Sn—In—Ag—Bi, Sn—Zn, Sn—Zn—Bi, Sn—Bi. It is desirable that the solder material is a medium-temperature to low-temperature solder material such as Sn-In or Sn-In. The bonding material disclosed in the present specification may include only one type of Sn alloy as the low melting point metal particles, or may include a plurality of types of Sn alloys.

低融点金属粒子は、Ｓｎ合金であり、その粒径が２０〜４０μｍであることが望ましい。粒径が２０μｍ未満であると、高融点金属粒子への濡れ拡がり性が低下し、リフロー後に接合材の表面に現れる高融点金属を覆いきれない可能性が残る。その結果、接合不良のおそれが生じる。粒径が４０μｍを超えると、接合材を基板に印刷するときの精度が低下するおそれが生じる。   The low melting point metal particles are an Sn alloy, and the particle size is desirably 20 to 40 μm. When the particle size is less than 20 μm, the wet-spreading property to the refractory metal particles is lowered, and there is a possibility that the refractory metal appearing on the surface of the bonding material after reflow cannot be covered. As a result, there is a risk of poor bonding. When the particle diameter exceeds 40 μm, there is a possibility that accuracy when the bonding material is printed on the substrate is lowered.

接合材に配合されるフラックス樹脂は、熱硬化性を有するエポキシ樹脂を含んでいるとよい。特に、フラックス樹脂は、エポキシ樹脂、活性剤、ロジン、チキソ剤、溶剤等を均一に混合したものを用いるのが好ましい。また、上記以外に、硬化促進剤、酸化防止剤、粉末表面処理剤、カップリング剤等を含んでいてもよく、これらはフラックス樹脂の樹脂組成に対して０．０１−５．０質量％の範囲であることが好ましい。   The flux resin blended in the bonding material may contain an epoxy resin having thermosetting properties. In particular, it is preferable to use a flux resin in which an epoxy resin, an activator, a rosin, a thixotropic agent, a solvent and the like are uniformly mixed. In addition to the above, a curing accelerator, an antioxidant, a powder surface treatment agent, a coupling agent and the like may be contained, and these are 0.01 to 5.0% by mass with respect to the resin composition of the flux resin. A range is preferable.

エポキシ樹脂については、特に制限はないが、例えばビスフェノールＡ型、ビスフェノールＦ型、ビフェニル型、ナフタレン型等のものが使用可能である。エポキシ樹脂は、常温で液状のものが好ましい。固形のものを使用する場合は、液状のものと併用することが好ましい。   Although there is no restriction | limiting in particular about an epoxy resin, For example, things, such as a bisphenol A type, a bisphenol F type, a biphenyl type, a naphthalene type, can be used. The epoxy resin is preferably liquid at room temperature. When using a solid thing, it is preferable to use together with a liquid thing.

活性剤は、金属表面に存在する金属酸化物を除去する作用を有するものであれば制限はないが、有機酸、非解離性のハロゲン化化合物からなる非解離型活性剤、アミン系活性剤などが好ましい。有機酸としては、コハク酸、グルタル酸、アジピン酸、ピコリン酸、６−メチルピコリン酸、３−シクロプロピルピコリン酸、５−ブチルピコリン酸、６−シクロブチルピコリン酸、安息香酸、「１，２−アミノドデカン酸」、セバシン酸、ジフェニル酢酸、「３，５−ジブロモサリチル酸」、ｐ−アニス酸などが挙げられる。   The activator is not limited as long as it has an action of removing a metal oxide present on the metal surface, but an organic acid, a non-dissociative activator composed of a non-dissociable halogenated compound, an amine activator, etc. Is preferred. Organic acids include succinic acid, glutaric acid, adipic acid, picolinic acid, 6-methylpicolinic acid, 3-cyclopropylpicolinic acid, 5-butylpicolinic acid, 6-cyclobutylpicolinic acid, benzoic acid, “1,2 -Aminododecanoic acid ", sebacic acid, diphenylacetic acid," 3,5-dibromosalicylic acid ", p-anisic acid and the like.

非解離性のハロゲン化化合物からなる非解離型活性剤としては、例えば、特開２０１５−１６０２３４号公報に記載されているような、ハロゲン原子が共有結合により結合した非塩系の有機化合物が挙げられる。このハロゲン化化合物としては、塩素化物、臭素化物、フッ化物のように塩素、臭素、フッ素の各単独元素の共有結合による化合物でもよいが、塩素、臭素およびフッ素の任意の２つまたは全部のそれぞれの共有結合を有する化合物でもよい。これらの化合物は、水性溶媒に対する溶解性を向上させるために、例えばハロゲン化アルコールやハロゲン化カルボキシルのように水酸基やカルボキシル基などの極性基を有することが好ましい。ハロゲン化アルコールとしては、例えば、２，３−ジブロモプロパノール／２，３−ジブロモブタンジオール／トランス−２，３−ジブロモ−２−ブテン−１，４−ジオール／１，４−ジブロモ−２−ブタノール／トリブロモネオペンチルアルコールなどの臭素化アルコール／１，３−ジクロロ−２−プロパノール／１，４−ジクロロ−２−ブタノールなどの塩素化アルコール／３−フルオロカテコールなどのフッ素化アルコール／その他これらに類する化合物が挙げられる。ハロゲン化カルボキシルとしては、２−ヨード安息香酸、３−ヨード安息香酸、２−ヨードプロピオン酸、５−ヨードサリチル酸、５−ヨードアントラニル酸などのヨウ化カルボキシル、２−クロロ安息香酸、３−クロロプロピオン酸などの塩化カルボキシル、２，３−ジブロモプロピオン酸、２，３−ジブロモコハク酸、２−ブロモ安息香酸などの臭素化カルボキシル、その他これらに類する化合物が挙げられる。これらの活性剤は、１種類を単独で用いてもよく、あるいは、２種類以上の活性剤を混合して用いてもよい。   Examples of the non-dissociative activator comprising a non-dissociable halogenated compound include non-salt organic compounds in which halogen atoms are bonded by a covalent bond as described in JP-A-2015-160234. It is done. The halogenated compound may be a compound formed by covalent bonding of chlorine, bromine and fluorine, such as chlorinated, brominated and fluoride, but any two or all of chlorine, bromine and fluorine may be used. The compound which has the following covalent bond may be sufficient. In order to improve the solubility in an aqueous solvent, these compounds preferably have a polar group such as a hydroxyl group or a carboxyl group such as a halogenated alcohol or a halogenated carboxyl. Examples of the halogenated alcohol include 2,3-dibromopropanol / 2,3-dibromobutanediol / trans-2,3-dibromo-2-butene-1,4-diol / 1,4-dibromo-2-butanol. / Brominated alcohol such as tribromoneopentyl alcohol / Chlorinated alcohol such as 1,3-dichloro-2-propanol / Chlorinated alcohol such as 1,4-dichloro-2-butanol / Fluorinated alcohol such as 3-fluorocatechol / etc. Similar compounds. Examples of the halogenated carboxyl include 2-iodobenzoic acid, 3-iodobenzoic acid, 2-iodopropionic acid, 5-iodosalicylic acid, 5-iodoanthranilic acid, etc., 2-chlorobenzoic acid, 3-chloropropion Examples thereof include carboxyl chloride such as acid, brominated carboxyl such as 2,3-dibromopropionic acid, 2,3-dibromosuccinic acid and 2-bromobenzoic acid, and other similar compounds. These activators may be used alone or in admixture of two or more activators.

アミン系活性剤としては、例えば、特開２０１５−１６０２３４号公報に記載されているような、下記の活性剤が挙げられる。アミン系活性剤としては、アミン類（エチレンジアミンなどのポリアミンなど）、アミン塩類（トリメチロールアミン、シクロヘキシルアミン、ジエチルアミンなどのアミンやアミノアルコールなどの有機酸塩や無機酸塩（塩酸、硫酸、臭化水素酸など））、アミノ酸類（グリシン、アラニン、アスパラギン酸、グルタミン酸、バリンなど）、アミド系化合物などが挙げられる。具体的には、ジフェニルグアニジン臭化水素酸塩、シクロヘキシルアミン臭化水素酸塩、ジエチルアミン塩（塩酸塩、コハク酸塩、アジピン酸塩、セバシン酸塩など）、トリエタノールアミン、モノエタノールアミン、これらのアミンの臭化水素酸塩などが挙げられる。これらの活性剤も、１種類を単独で用いてもよく、あるいは、２種類以上の活性剤を混合して用いてもよい。   Examples of the amine-based activator include the following activators as described in JP-A-2015-160234. Amine-based activators include amines (such as polyamines such as ethylenediamine), amine salts (such as amines such as trimethylolamine, cyclohexylamine, and diethylamine) and organic acid salts and inorganic acid salts such as amino alcohols (hydrochloric acid, sulfuric acid, bromide). Hydroacid, etc.), amino acids (glycine, alanine, aspartic acid, glutamic acid, valine, etc.), amide compounds and the like. Specifically, diphenylguanidine hydrobromide, cyclohexylamine hydrobromide, diethylamine salt (hydrochloride, succinate, adipate, sebacate, etc.), triethanolamine, monoethanolamine, etc. And the hydrobromide of the amine. These activators may be used alone or in admixture of two or more activators.

活性剤は、フラックス樹脂の組成に対して０．５〜１０．０質量％の範囲で混合するのが好ましい。０．５％未満では低融点金属粒子の溶解後の濡れ性が低下し、焼結性が不足する傾向がある。また、１０質量％を超えると、フラックス組成物の絶縁性が低下する傾向がある。   The activator is preferably mixed in the range of 0.5 to 10.0% by mass with respect to the composition of the flux resin. If it is less than 0.5%, the wettability after dissolution of the low melting point metal particles tends to decrease, and the sinterability tends to be insufficient. Moreover, when it exceeds 10 mass%, there exists a tendency for the insulation of a flux composition to fall.

ロジンについては、カルボキシル基を有する松脂などの天然ロジン、重合ロジンであれば、特に制限はない。例えば、アビエチン酸、ネオアビエチン酸、パラストリン酸、ピマール酸、イソピマール酸、デヒドロアビエチン酸などの天然ロジンや、アクリル化ロジン、水添ロジン、マレイン化ロジン等の重合ロジンが好ましい。これらのロジンは１種類を単独で用いてもよく、２種類以上を混合して用いてもよい。   The rosin is not particularly limited as long as it is a natural rosin such as pine resin having a carboxyl group or a polymerized rosin. For example, natural rosins such as abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, and dehydroabietic acid, and polymerized rosins such as acrylated rosin, hydrogenated rosin and maleated rosin are preferred. These rosins may be used alone or in combination of two or more.

溶剤については、比較的に高沸点で水溶性の溶剤を用いることが好ましい。例えば、特開２０１５−１６０２３４号公報に記載された、次の溶剤が挙げられる。そのような溶剤としては、沸点１７０℃以上の水溶性溶剤を用いることが好ましい。そのような溶剤としては、例えば、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ヘキシレングリコール、ヘキシルジグリコール、１,５−ペンタンジオール、メチルカルビトール、ブチルカルビトール、２−エチルヘキシルジグリコール（ＥＨＤＧ）、オクタンジオール、フェニルグリコール、ジエチレングリコールモノヘキシルエーテル、テトラエチレングリコールジメチルエーテルが挙げられる。これらの溶剤は１種を単独で用いてもよく、２種以上を混合して用いてもよい。   As for the solvent, it is preferable to use a water-soluble solvent having a relatively high boiling point. For example, the following solvents described in JP-A-2015-160234 can be mentioned. As such a solvent, a water-soluble solvent having a boiling point of 170 ° C. or higher is preferably used. Examples of such a solvent include diethylene glycol, dipropylene glycol, triethylene glycol, hexylene glycol, hexyl diglycol, 1,5-pentanediol, methyl carbitol, butyl carbitol, and 2-ethylhexyl diglycol (EHDG). , Octanediol, phenyl glycol, diethylene glycol monohexyl ether, and tetraethylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more.

酸化防止剤については、フラックス中に含まれていてもよく、フェノール系酸化防止剤、硫黄系酸化防止剤などが挙げられる。フェノール系酸化防止剤としては、分子内に置換または無置換のフェノール基を有するフェノール系酸化防止剤であり、ヒンダードフェノール構造またはハーフヒンダードフェノール構造を有するものであってよい。硫黄系酸化防止剤としては、分子内に硫黄およびエステル結合を有するチオエステル系酸化防止剤などが挙げられる。これらの酸化防止剤は、１種類を単独で用いてもよく、２種類以上を混合して用いてもよい。   The antioxidant may be contained in the flux, and examples thereof include a phenolic antioxidant and a sulfurous antioxidant. As a phenolic antioxidant, it is a phenolic antioxidant which has a substituted or unsubstituted phenol group in a molecule | numerator, and may have a hindered phenol structure or a half hindered phenol structure. Examples of the sulfur-based antioxidant include a thioester-based antioxidant having sulfur and an ester bond in the molecule. These antioxidants may be used alone or in combination of two or more.

導電性の接合材のペースト中の金属粒子とフラックス樹脂の割合は、金属の組成および粒径、フラックス樹脂の種類などに適合させて適切な範囲から選択可能であり、ペースト全体（接合材全体）の質量に対して、金属粒子が８５〜９５質量％が好ましく、８８〜９３質量％であることが特に好ましい。８５質量％未満では、接合材の印刷形状不良や、加熱時のダレ等が発生する。また、９５質量％を超えると、フラックス樹脂中に金属粒子が十分に混合しなくなる。   The ratio of metal particles and flux resin in the conductive bonding material paste can be selected from an appropriate range according to the metal composition and particle size, type of flux resin, etc., and the entire paste (the entire bonding material) The metal particles are preferably 85 to 95% by mass and particularly preferably 88 to 93% by mass with respect to the mass. If the amount is less than 85% by mass, the printed material of the bonding material may be defective in shape or sag during heating. On the other hand, if it exceeds 95% by mass, the metal particles are not sufficiently mixed in the flux resin.

本明細書が開示する接合材を用いて、表面実装用の部品をプリント基板に接合することも好適である。プリント基板の材料としては、紙フェノール系、ガラスエポキシ系、ポリイミド系、ビスマレイミドトリアジン系、液晶ポリマー系、ポリテトラフルオロエチレンおよびポリエーテルエーテルケトン等の熱硬化樹脂系、セラミック系、金属系を使用したものを用いてもよい。表面実装用の部品は、チップ部品、半導体部品、小型実装部品のいずれでもよい。チップ部品の例は、コンデンサ、抵抗、ダイオードなどの電子部品である。半導体部品の例は、ＱＦＰ（Quad Flat Package）、ＴＳＯＰ（Thin Small Outline Package）、ＳＯＰ（Small Outline Package）、ＣＳＰ（Chip Size Package）、ＢＧＡ（Ball Grid Array）などがある。小型実装部品の例は、アルミ電解コンデンサ、トランジスタ、トリマ、リレー、トランスなどがある。   It is also preferable to bond a component for surface mounting to a printed board using the bonding material disclosed in this specification. As materials for printed circuit boards, paper phenol, glass epoxy, polyimide, bismaleimide triazine, liquid crystal polymer, thermosetting resin such as polytetrafluoroethylene and polyetheretherketone, ceramic, and metal are used. You may use what you did. The surface mounting component may be a chip component, a semiconductor component, or a small mounting component. Examples of chip components are electronic components such as capacitors, resistors, and diodes. Examples of semiconductor components include QFP (Quad Flat Package), TSOP (Thin Small Outline Package), SOP (Small Outline Package), CSP (Chip Size Package), and BGA (Ball Grid Array). Examples of small mounting parts include aluminum electrolytic capacitors, transistors, trimmers, relays, and transformers.

図３に、本明細書が開示する接合材を用いた部品実装工程の説明図を示す。図３（Ａ）は、回路基板３にペースト状の接合材２の印刷工程を説明する図である。導電性のペースト状の接合材２は、メタルマスクなどを用いて回路基板３の上の銅配線４の上に印刷される。図３（Ｂ）は、部品の載置工程を説明する図である。チップ部品５は、電子部品実装機（チップマウンタ）等で、印刷された接合材２の上に実装される。図３（Ｃ）は、リフロー工程を説明する図である。図３（Ｃ）は、リフロー加熱後の基板を示している。チップ部品５を実装した回路基板３は、リフロー炉などで加熱することで、接合材２が合金化し、全体がペースト状から固化し、実装が完了する。なお、図３（Ｃ）では、接合材２が図３（Ｂ）の状態から変化し、合金化したことを模式的に表すために、接合材２にハッチングを施してある。   FIG. 3 is an explanatory diagram of a component mounting process using the bonding material disclosed in this specification. FIG. 3A is a diagram illustrating a printing process of the paste-like bonding material 2 on the circuit board 3. The conductive paste-like bonding material 2 is printed on the copper wiring 4 on the circuit board 3 using a metal mask or the like. FIG. 3B is a diagram illustrating a component placing process. The chip component 5 is mounted on the printed bonding material 2 by an electronic component mounting machine (chip mounter) or the like. FIG. 3C illustrates the reflow process. FIG. 3C shows the substrate after reflow heating. The circuit board 3 on which the chip component 5 is mounted is heated in a reflow furnace or the like, whereby the bonding material 2 is alloyed and the whole is solidified from a paste form, and the mounting is completed. In FIG. 3C, the bonding material 2 is hatched to schematically show that the bonding material 2 has changed from the state of FIG. 3B and has been alloyed.

２回のリフローを行って半導体モジュール実装基板や部品内蔵基板などの部品実装を行う場合において、本明細書が開示する接合材を１次リフローに用いると、次の利点が得られる。
（１）従来よりも低温（≦２６０℃）で部品を実装可能である。
（２）２次リフロー（約２６０℃）の際に再溶融しない。
（３）環境への負荷が小さい（Ｐｂフリーに対応）。
（４）接合部からウィスカが発生しない。ウィスカが発生しないので、接合後の接合箇所に絶縁樹脂などのコーティング剤を塗布する必要がなくなる。 In the case where component mounting such as a semiconductor module mounting substrate or a component built-in substrate is performed by performing reflow twice, the following advantages can be obtained by using the bonding material disclosed in this specification for primary reflow.
(1) The component can be mounted at a lower temperature (≦ 260 ° C.) than in the past.
(2) Does not remelt during secondary reflow (about 260 ° C.).
(3) The load on the environment is small (corresponding to Pb free).
(4) No whisker is generated from the joint. Since the whisker does not occur, it is not necessary to apply a coating agent such as an insulating resin to the joined portion after joining.

以下、実施例を説明する。配合を変えて９種類の評価サンプルと３種類の比較例を作成し、（１）再溶融するか否か、（２）せん断強度、（３）ウィスカの発生の有無、を評価した。実施方法は以下の通りである。図４、図５に、実施例１−９と比較例１−３の組成と評価結果（特性）を示す。   Examples will be described below. Nine kinds of evaluation samples and three kinds of comparative examples were prepared by changing the composition, and (1) whether or not to remelt, (2) shear strength, and (3) presence or absence of whisker generation were evaluated. The implementation method is as follows. 4 and 5 show the compositions and evaluation results (characteristics) of Example 1-9 and Comparative Example 1-3.

＜フラックス樹脂の調整＞（手法は共有）
液状エポキシ樹脂（製品名「jER828」／「jER806」、ビスフェノールＡ型／Ｆ型エポシキ樹脂、三菱化学（株）製）、ロジン（デヒドロアビエチン酸）、活性剤（グルタル酸）、チキソ剤（１，２−ヒドロキシステアリン酸トリグリセリド）、溶剤（ブチルカルビトール）を良く混合し、フラックス樹脂を調整した。 <Adjustment of flux resin> (Method is shared)
Liquid epoxy resin (product name “jER828” / “jER806”, bisphenol A / F type epoxy resin, manufactured by Mitsubishi Chemical Corporation), rosin (dehydroabietic acid), activator (glutaric acid), thixotropic agent (1, 2-hydroxystearic acid triglyceride) and a solvent (butyl carbitol) were mixed well to prepare a flux resin.

＜導電性ペースト（接合材）の調整＞（手法は共通）
フラックス樹脂と市販の銅粉末（平均粒径１０μｍ）とはんだ粉末（ＳＡＣ３０５、平均粒径３０μｍ）とをソフナーで混練し、導電性ペーストの接合材を調整した。ＳＡＣ３０５は、合金の組成がＳｎ−３．０Ａｇ−０．５Ｃｕのはんだ材である。 <Adjustment of conductive paste (bonding material)> (Method is common)
Flux resin, commercially available copper powder (average particle size 10 μm) and solder powder (SAC305, average particle size 30 μm) were kneaded with a softener to prepare a bonding material for the conductive paste. SAC305 is a solder material whose alloy composition is Sn-3.0Ag-0.5Cu.

＜評価サンプル（実施例と比較例）作成＞
表面に銅箔ランドが形成されたガラスエポキシ基板の上に上記した接合材を、０．８ｍｍ×１．５ｍｍ×１００μｍのメタルマスクを用いてメタルスキージで印刷した。その後、Ｓｎめっきの１００５チップを銅箔ランドの印刷膜上に２０個搭置した。プリヒート１８０℃、ピーク温度２５０℃のリフロー条件でチップ部品を実装し、評価サンプルとした。 <Creation of evaluation samples (Examples and Comparative Examples)>
The above-mentioned bonding material was printed on a glass epoxy substrate having a copper foil land formed on the surface using a metal mask of 0.8 mm × 1.5 mm × 100 μm with a metal squeegee. After that, 20 Sn-plated 1005 chips were placed on the printed film of the copper foil land. Chip components were mounted under reflow conditions of preheating 180 ° C. and peak temperature 250 ° C. to obtain evaluation samples.

＜２６０℃での再溶融評価＞
作成した評価サンプルを２６０℃に設定したはんだ槽に１分間浮かべ、接合部が再溶融したか否かを目視で観察した。 <Remelting evaluation at 260 ° C.>
The prepared evaluation sample was floated in a solder bath set at 260 ° C. for 1 minute, and it was visually observed whether or not the joint portion was remelted.

＜せん断強度評価＞
作成した評価サンプルをシェアテスタ（「万能型ボンドテスター４０００」、デイジ・ジャパン（株）製）を用いて、チップ接合部のせん断強度を測定した。 <Evaluation of shear strength>
A shear tester (“Universal Bond Tester 4000”, manufactured by Daisy Japan Co., Ltd.) was used to measure the shear strength of the chip joint.

＜ウィスカの発生評価＞
作成した評価サンプルを８５℃、８５ＲＨの高温高湿条件に２００時間投入し、その後常温で２４時間放置する。これを５回繰り返した後、顕微鏡でウィスカが発生しているか否かを観察した。上記条件の５回の繰り返しは、高温高湿放置１０００時間に相当する。 <Evaluation of whisker generation>
The prepared evaluation sample is put in high-temperature and high-humidity conditions of 85 ° C. and 85 RH for 200 hours, and then left at room temperature for 24 hours. After repeating this five times, it was observed with a microscope whether or not whiskers were generated. Five repetitions of the above conditions are equivalent to 1000 hours at high temperature and high humidity.

実施例１−９と比較例１―３の組成の技術的意味は以下の通りである。
実施例１：標準組成（Ｃｕ粒子の含有比率：６５Wt％）
実施例２：Ｃｕ粒子の質量比の下限（Ｃｕ粒子の含有比率：５５Wt％）
実施例３：Ｃｕ粒子の質量比の上限（Ｃｕ粒子の含有比率：７５Wt％）
実施例４：Ｃｕ粒子に代えてＡｇ粒子を採用
実施例５：Ｃｕ粒子の表面にＳｎめっき有
実施例６：はんだ粉末ＳＡＣ３０５と、Ｓｎ−Ｂｉ粒子の混合組成
実施例７：フラックスの組成比を変更
実施例８：エポキシ樹脂を２種類混合
実施例９：金属とフラックスの混合比を変更
比較例１：Ｃｕ粒子含有量過少（Ｃｕ粒子の含有比率：５０Wt％）
比較例２：Ｃｕ粒子含有量過多（Ｃｕ粒子の含有比率：８０Wt％）
比較例３：エポキシ樹脂無 The technical meanings of the compositions of Example 1-9 and Comparative Example 1-3 are as follows.
Example 1: Standard composition (Cu particle content ratio: 65 Wt%)
Example 2: Lower limit of mass ratio of Cu particles (Cu particle content ratio: 55 Wt%)
Example 3: Upper limit of mass ratio of Cu particles (Cu particle content ratio: 75 Wt%)
Example 4: Adopting Ag particles instead of Cu particles Example 5: Sn plating provided on the surface of Cu particles Example 6: Mixed composition of solder powder SAC305 and Sn-Bi particles Example 7: Composition ratio of flux Modified Example 8: Mixing two kinds of epoxy resins Example 9: Changing the mixing ratio of metal and flux Comparative Example 1: Cu content too low (Cu particle content ratio: 50 Wt%)
Comparative Example 2: Excess Cu particle content (Cu particle content ratio: 80 Wt%)
Comparative Example 3: No epoxy resin

評価結果も図４、図５に示してある。図４、図５の結果から、実施例１−９は、２６０℃での再溶融はなく、ウィスカの発生もなかった。実施例１−９では、せん断強度は１４．６〜１７．０［Ｎ］の良好な強度が得られた。これらの実施例に対して、Ｃｕ粒子の組成比が５０質量％の比較例１は、Ｃｕ粒子の組成比が低いために、リフロー後にはんだ材ＳＡＣ３０５（Ｓｎ）の残存によるウィスカの発生が見られた。   The evaluation results are also shown in FIGS. From the results of FIGS. 4 and 5, Example 1-9 had no remelting at 260 ° C. and no whisker was generated. In Example 1-9, good strength of 14.6 to 17.0 [N] was obtained as the shear strength. In contrast to these examples, in Comparative Example 1 in which the composition ratio of the Cu particles is 50 mass%, the composition ratio of the Cu particles is low, so that whisker is generated due to the remaining solder material SAC305 (Sn) after reflow. It was.

また、Ｃｕ粒子の組成比が８０質量％の比較例２は、はんだ材ＳＡＣ３０５が不足するため、せん断強度が大幅に低下した。さらに、Ｃｕ粒子が比較的に多く、また、フラックス組成中にエポキシ樹脂を含有していない比較例３は、フラックス樹脂が熱硬化しないため、せん断強度の低下がみられた。   Further, in Comparative Example 2 in which the composition ratio of the Cu particles was 80% by mass, the shear strength was greatly reduced because the solder material SAC305 was insufficient. Further, in Comparative Example 3 in which the number of Cu particles is relatively large and the epoxy resin is not included in the flux composition, the shear strength is reduced because the flux resin is not thermally cured.

高融点金属粒子（Ｃｕ粒子）と低融点金属粒子（はんだ材ＳＡＣ３０５）の総質量に対する高融点金属粒子（Ｃｕ粒子）の質量割合は、５５％（実施例２）〜７５％（実施例３）で良好な結果が得られている。特に、高融点金属粒子（Ｃｕ粒子）の質量割合が６５％（実施例１、４−９）〜７５％（実施例３）で良好な結果が得られた。   The mass ratio of the high melting point metal particles (Cu particles) to the total mass of the high melting point metal particles (Cu particles) and the low melting point metal particles (solder material SAC305) is 55% (Example 2) to 75% (Example 3). Good results have been obtained. In particular, good results were obtained when the mass ratio of the refractory metal particles (Cu particles) was 65% (Examples 1 and 4-9) to 75% (Example 3).

実施例で説明した技術に関する留意点を述べる。上記の記載中に使用した金属記号の意味を以下に記す。Ｃｕ：銅、Ｓｎ：スズ、Ａｌ：アルミニウム、Ａｕ：金、Ａｇ：銀、Ｂｉ：ビスマス、Ｉｎ：インジウム、Ｚｎ：亜鉛である。   Points to be noted regarding the technology described in the embodiments will be described. The meanings of the metal symbols used in the above description are described below. Cu: copper, Sn: tin, Al: aluminum, Au: gold, Ag: silver, Bi: bismuth, In: indium, Zn: zinc.

以上、本発明の具体例を詳細に説明したが、これらは例示に過ぎず、特許請求の範囲を限定するものではない。特許請求の範囲に記載の技術には、以上に例示した具体例を様々に変形、変更したものが含まれる。本明細書または図面に説明した技術要素は、単独であるいは各種の組合せによって技術的有用性を発揮するものであり、出願時請求項記載の組合せに限定されるものではない。また、本明細書または図面に例示した技術は複数目的を同時に達成し得るものであり、そのうちの一つの目的を達成すること自体で技術的有用性を持つものである。   Specific examples of the present invention have been described in detail above, but these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above. The technical elements described in this specification or the drawings exhibit technical usefulness alone or in various combinations, and are not limited to the combinations described in the claims at the time of filing. In addition, the technology exemplified in this specification or the drawings can achieve a plurality of objects at the same time, and has technical usefulness by achieving one of the objects.

Claims (6)

高融点金属粒子と、低融点金属粒子と、熱硬化性を有するフラックス樹脂を含んでいる接合材であり、
前記高融点金属粒子と前記低融点金属粒子の総質量に対する前記高融点金属粒子の質量割合が５５〜７５％である、接合材。 It is a bonding material containing high melting point metal particles, low melting point metal particles, and a thermosetting flux resin,
The bonding material, wherein a mass ratio of the high melting point metal particles to a total mass of the high melting point metal particles and the low melting point metal particles is 55 to 75%. 前記高融点金属粒子の前記質量割合が６５〜７５％である、請求項１に記載の接合材。   The bonding material according to claim 1, wherein the mass ratio of the refractory metal particles is 65 to 75%. 前記高融点金属粒子は、Ｃｕ、Ｃｕ合金、Ａｌ、Ａｇ、Ａｕのいずれかであり、その粒径が５〜３０μｍである、請求項１または２に記載の接合材。   The bonding material according to claim 1, wherein the refractory metal particles are any one of Cu, Cu alloy, Al, Ag, and Au, and the particle diameter thereof is 5 to 30 μm. 前記低融点金属粒子は、Ｓｎ合金であり、その粒径が２０〜４０μｍである、請求項１から３のいずれか１項に記載の接合材。   The bonding material according to any one of claims 1 to 3, wherein the low-melting-point metal particles are an Sn alloy and have a particle size of 20 to 40 µm. 前記高融点金属粒子の表面がＳｎまたはＳｎ合金でめっきされている、請求項１から３のいずれか１項に記載の接合材。   The bonding material according to any one of claims 1 to 3, wherein a surface of the refractory metal particles is plated with Sn or an Sn alloy. 前記フラックス樹脂は、エポキシ樹脂を含んでいる、請求項１から５のいずれか１項に記載の接合材。   The bonding material according to claim 1, wherein the flux resin includes an epoxy resin.
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